Análise wavelet em curvas de luz estelares de sistemas binários da missão espacial CoRoT

Binary systems are key environments to study the fundamental properties of stars. In this work, we analyze 99 binary systems identified by the CoRoT space mission. From the study of the phase diagrams of these systems, our sample is divided into three groups: those whose systems are characterized by the variability relative to the binary eclipses; those presenting strong modulations probably due to the presence of stellar spots on the surface of star; and those whose systems have variability associated with the expansion and contraction of the surface layers. For eclipsing binary stars, phase diagrams are used to estimate the classification in regard to their morphology, based on the study of equipotential surfaces. In this context, to determine the rotation period, and to identify the presence of active regions, and to investigate if the star exhibits or not differential rotation and study stellar pulsation, we apply the wavelet procedure. The wavelet transform has been used as a powerful tool in the treatment of a large number of problems in astrophysics. Through the wavelet transform, one can perform an analysis in time-frequency light curves rich in details that contribute significantly to the study of phenomena associated with the rotation, the magnetic activity and stellar pulsations. In this work, we apply Morlet wavelet (6th order), which offers high time and frequency resolution and obtain local (energy distribution of the signal) and global (time integration of local map) wavelet power spectra. Using the wavelet analysis, we identify thirteen systems with periodicities related to the rotational modulation, besides the beating pattern signature in the local wavelet map of five pulsating stars over the entire time span.

Análise wavelet em curvas de luz estelares de sistemas binários da missão espacial CoRoT

Binary systems are key environments to study the fundamental properties of stars. In this work, we analyze 99 binary systems identified by the CoRoT space mission. From the study of the phase diagrams of these systems, our sample is divided into three groups: those whose systems are characterized by the variability relative to the binary eclipses; those presenting strong modulations probably due to the presence of stellar spots on the surface of star; and those whose systems have variability associated with the expansion and contraction of the surface layers. For eclipsing binary stars, phase diagrams are used to estimate the classification in regard to their morphology, based on the study of equipotential surfaces. In this context, to determine the rotation period, and to identify the presence of active regions, and to investigate if the star exhibits or not differential rotation and study stellar pulsation, we apply the wavelet procedure. The wavelet transform has been used as a powerful tool in the treatment of a large number of problems in astrophysics. Through the wavelet transform, one can perform an analysis in time-frequency light curves rich in details that contribute significantly to the study of phenomena associated with the rotation, the magnetic activity and stellar pulsations. In this work, we apply Morlet wavelet (6th order), which offers high time and frequency resolution and obtain local (energy distribution of the signal) and global (time integration of local map) wavelet power spectra. Using the wavelet analysis, we identify thirteen systems with periodicities related to the rotational modulation, besides the beating pattern signature in the local wavelet map of five pulsating stars over the entire time span.

Metamorphic investigation of mid-P aluminous gneisses from the central Grenville Province

This is a metamorphic study of mid-P anatectic aluminous gneisses from the Manicouagan and lac du Milieu areas of the central Grenville Province. The rocks are derived from hydrothermally altered felsic protoliths and were metamorphosed at granulite facies conditions during the Grenvillian orogeny. The samples come from three locations separated by several tens of kilometers and exhibit a wide range of textures and bulk compositions. However, they all have the same peak mineral assemblage: garnet + biotite + quartz + K-feldspar +/- plagioclase +/- sillimanite with retrograde cordierite in some, and show evidence of partial melting and melt loss. In terms of mineralogy and bulk composition, the samples were divided into two groups, sillimanite-rich and sillimanite-poor, with a high and low Alumina index in the AFM space, respectively. Phase equilibria modeling in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O– TiO₂–O (NCKFMASTHO) system using Thermocalc constrained the P–T field of the peak mineral assemblage at 800–900ºC and 6–11kbar, with melt solidification in the range of 800–865ºC and 6–8kbar. The presence of sillimanite inclusions in garnet, and of only scarce, retrograde cordierite, is consistent with moderate dP/dT gradient ‘hairpin’ P– T paths, which were similar between the three locations. This study also investigated the role of Fe3+ on phase stability in mid-P aluminous systems. Fe³⁺ is problematic because although it is incorporated in the NaCKFMASTHO system, it is rarely measured in modeled minerals and rocks and its value is generally assumed. Biotite may contain significant amounts of Fe³⁺, and these were analysed by Mössbauer spectroscopy in selected samples, where they were found to be low (0-4%). In addition, the effect of increasing the bulk Fe³⁺ in the mid-P portion of phase diagrams was modeled. This increase added new minor phases and changed the phase proportions, as well as shifted phase boundaries to a small degree, but P–T paths remained largely unaffected. Finally, the two methods commonly used in phase equilibria modeling to account for melt loss were compared. In some cases there were major differences in the topologies between the ‘melt reintegration’ and ‘adding water’ methods, but the former method is the most consistent with the rock data, and should be the method of choice.

Ionic liquids as modulators of fragrance release in consumer goods

When organic esters or alcohols were dissolved in each of three novel ionic liquids (which have no effective vapour pressure), the vapour–liquid equilibria (as measured by infrared spectroscopy of the gas phase) revealed significant positive deviation from Raoult’s law for a wide range of perfume raw materials. The addition of water amplified the repulsive effect of the ionic liquid matrix, and this was exemplified by a series of ternary phase diagrams

Shapes and Dynamics of Blood Cells in Poiseuille and Shear Flows

The dynamics, shape, deformation, and orientation of red blood cells in microcirculation affect the rheology, flow resistance and transport properties of whole blood. This leads to important correlations of cellular and continuum scales. Furthermore, the dynamics of RBCs subject to different flow conditions and vessel geometries is relevant for both fundamental research and biomedical applications (e.g drug delivery). In this thesis, the behaviour of RBCs is investigated for different flow conditions via computer simulations. We use a combination of two mesoscopic particle-based simulation techniques, dissipative particle dynamics and smoothed dissipative particle dynamics. We focus on the microcapillary scale of several μm. At this scale, blood cannot be considered at the continuum but has to be studied at the cellular level. The connection between cellular motion and overall blood rheology will be investigated. Red blood cells are modelled as viscoelastic objects interacting hydrodynamically with a viscous fluid environment. The properties of the membrane, such as resistance against bending or shearing, are set to correspond to experimental values. Furthermore, thermal fluctuations are considered via random forces. Analyses corresponding to light scattering measurements are performed in order to compare to experiments and suggest for which situations this method is suitable. Static light scattering by red blood cells characterises their shape and allows comparison to objects such as spheres or cylinders, whose scattering signals have analytical solutions, in contrast to those of red blood cells. Dynamic light scattering by red blood cells is studied concerning its suitability to detect and analyse motion, deformation and membrane fluctuations. Dynamic light scattering analysis is performed for both diffusing and flowing cells. We find that scattering signals depend on various cell properties, thus allowing to distinguish different cells. The scattering of diffusing cells allows to draw conclusions on their bending rigidity via the effective diffusion coefficient. The scattering of flowing cells allows to draw conclusions on the shear rate via the scattering amplitude correlation. In flow, a RBC shows different shapes and dynamic states, depending on conditions such as confinement, physiological/pathological state and cell age. Here, two essential flow conditions are studied: simple shear flow and tube flow. Simple shear flow as a basic flow condition is part of any more complex flow. The velocity profile is linear and shear stress is homogeneous. In simple shear flow, we find a sequence of different cell shapes by increasing the shear rate. With increasing shear rate, we find rolling cells with cup shapes, trilobe shapes and quadrulobe shapes. This agrees with recent experiments. Furthermore, the impact of the initial orientation on the dynamics is studied. To study crowding and collective effects, systems with higher haematocrit are set up. Tube flow is an idealised model for the flow through cylindric microvessels. Without cell, a parabolic flow profile prevails. A single red blood cell is placed into the tube and subject to a Poiseuille profile. In tube flow, we find different cell shapes and dynamics depending on confinement, shear rate and cell properties. For strong confinements and high shear rates, we find parachute-like shapes. Although not perfectly symmetric, they are adjusted to the flow profile and maintain a stationary shape and orientation. For weak confinements and low shear rates, we find tumbling slippers that rotate and moderately change their shape. For weak confinements and high shear rates, we find tank-treading slippers that oscillate in a limited range of inclination angles and strongly change their shape. For the lowest shear rates, we find cells performing a snaking motion. Due to cell properties and resultant deformations, all shapes differ from hitherto descriptions, such as steady tank-treading or symmetric parachutes. We introduce phase diagrams to identify flow regimes for the different shapes and dynamics. Changing cell properties, the regime borders in the phase diagrams change. In both flow types, both the viscosity contrast and the choice of stress-free shape are important. For in vitro experiments, the solvent viscosity has often been higher than the cytosol viscosity, leading to a different pattern of dynamics, such as steady tank-treading. The stress-free state of a RBC, which is the state at zero shear stress, is still controversial, and computer simulations enable direct comparisons of possible candidates in equivalent flow conditions.

Topics in equilibrium and nonequilibrium thermodynamics: computing crystalline free energies and engineering Maxwell’s demon.

This dissertation covers two separate topics in statistical physics. The first part of the dissertation focuses on computational methods of obtaining the free energies (or partition functions) of crystalline solids. We describe a method to compute the Helmholtz free energy of a crystalline solid by direct evaluation of the partition function. In the many-dimensional conformation space of all possible arrangements of N particles inside a periodic box, the energy landscape consists of localized islands corresponding to different solid phases. Calculating the partition function for a specific phase involves integrating over the corresponding island. Introducing a natural order parameter that quantifies the net displacement of particles from lattices sites, we write the partition function in terms of a one-dimensional integral along the order parameter, and evaluate this integral using umbrella sampling. We validate the method by computing free energies of both face-centered cubic (FCC) and hexagonal close-packed (HCP) hard sphere crystals with a precision of $10^{-5}k_BT$ per particle. In developing the numerical method, we find several scaling properties of crystalline solids in the thermodynamic limit. Using these scaling properties, we derive an explicit asymptotic formula for the free energy per particle in the thermodynamic limit. In addition, we describe several changes of coordinates that can be used to separate internal degrees of freedom from external, translational degrees of freedom. The second part of the dissertation focuses on engineering idealized physical devices that work as Maxwell's demon. We describe two autonomous mechanical devices that extract energy from a single heat bath and convert it into work, while writing information onto memory registers. Additionally, both devices can operate as Landauer's eraser, namely they can erase information from a memory register, while energy is dissipated into the heat bath. The phase diagrams and the efficiencies of the two models are solved and analyzed. These two models provide concrete physical illustrations of the thermodynamic consequences of information processing.

Coupling of magnetic, strain and electric polarization fields in the structure of multiferroic material

The comprehensive study on the coupling of magnetism, electrical polarization and the crystalline lattice with the off-stoichiometric effects in self-doped multiferroic hexagonal h-LuMnxO3±δ (0.92≤x≤1.12) ceramic oxides was carried out for the PhD work. There is a complex coupling of the three ferroic degrees. The cancelation of the magnetic moments of ions in the antiferromagnetic order, electric polarization with specific vortex/antivortex topology and lattice properties have pushed researchers to find out ways to disclose the underlying physics and chemistry of magneto-electric and magneto-elastic couplings of h-RMnO3 multiferroic materials. In this research work, self-doping of Lu-sites or Mn-sites of h-LuMnxO3±δ ceramics prepared via solid state route was done to pave a way for deeper understanding of the antiferromagnetic transition, the weak ferromagnetism often reported in the same crystalline lattices and the ferroelectric properties coupled to the imposed lattice changes. Accordingly to the aim of the PhD thesis, the objectives set for the sintering study in the first chapter on experimental results were two. First, study of sintering off-stoichiometric samples within conditions reported in the bibliography and also extracted from the phase diagrams of the LuMnxO3±δ, with a multiple firings ending with a last high temperature step at 1300ºC for 24 hours. Second, explore longer annealing times of up to 240 hours at the fixed temperature of 1300 ºC in a search for improving the properties of the solid solution under study. All series of LuMnxO3±δ ceramics for each annealing time were characterized to tentatively build a framework enabling comparison of measured properties with results of others available in literature. XRD and Rietveld refinement of data give the evolution the lattice parameters as a function to x. Shrinkage of the lattice parameters with increasing x values was observed, the stability limit of the solid solution being determined by analysis of lattice parameters. The evolution of grain size and presence of secondary phases have been investigated by means of TEM, SEM, EDS and EBSD techniques. The dependencies of grain growth and regression of secondary phases on composition x and time were further characterized. Magnetic susceptibility of samples and magnetic irreversibility were extensively examined in the present work. The dependency of magnetic susceptibility, Neel ordering transition and important magnetic parameters are determined and compared to observation in other multiferroics in the following chapter of the thesis. As a tool of high sensitivity to detect minor traces of the secondary phase hausmannite, magnetic measurements are suggested for cross-checking of phase diagrams. Difficulty of previous studies on interpreting the magnetic anomaly below 43 K in h-RMnO3 oxides was discussed and assigned to the Mn3O4 phase, with supported of the electron microscopy. Magneto-electric coupling where AFM ordering is coupled to dielectric polarization is investigated as a function of x and of sintering condition via frequency and temperature dependent complex dielectric constant measurements in the final chapter of the thesis. Within the limits of solid solubility, the crystalline lattice of off-stoichiometric ceramics was shown to preserve the magneto-electric coupling at TN. It represents the first research work on magneto-electric coupling modified by vacancy doping to author’s knowledge. Studied lattices would reveal distortions at the atomic scale imposed by local changes of x dependent on sintering conditions which were widely inspected by using TEM/STEM methods, complemented with EDS and EELS spectroscopy all together to provide comprehensive information on cross coupling of distortions, inhomogeneity and electronic structure assembled and discussed in a specific chapter. Internal interfaces inside crystalline grains were examined. Qualitative explanations of the measured magnetic and ferroelectric properties were established in relation to observed nanoscale features of h-LuMnxO3±δ ceramics. Ferroelectric domains and topological defects are displayed both in TEM and AFM/PFM images, the later technique being used to look at size, distribution and switching of ferroelectric domains influenced by vacancy doping at the micron scale bridging to complementary TEM studies on the atomic structure of ferroelectric domains. In support to experimental study, DFT simulations using Wien2K code have been carried out in order to interpret the results of EELS spectra of O K-edge and to obtain information on the cation hybridization to oxygen ions. The L3,2 edges of Mn is used to access the oxidation state of the Mn ions inside crystalline grains. In addition, rehybridization driven ferroelectricity is also evaluated by comparing the partial density of states of the orbitals of all ions of the samples, also the polarization was calculated and correlated to the off-stoichiometric effect.

Extraction and purification of theobromine using ionic liquids

Theobromine is an alkaloid present in cocoa and it is used in the treatment of atherosclerosis, hypertension, angina, among others. Due to its importance, the aim of this work consists on the development of an efficient and sustainable technology for the extraction of theobromine from cocoa beans. For the development of a purification technique for theobromine extracted from cocoa, aqueous biphasic systems (ABS) composed of ionic liquids (ILs) were initially studied to infer on the most promising systems. Cholinium-based ILs, based on a non-toxic and biocompatible cation, were used combined with two polymers (PPG 400 and PEG 400) and an inorganic salt (K3PO4). The respective phase diagrams at 298 K and atmospheric pressure were determined, as well as their extraction efficiencies for theobromine. The results obtained indicate that K3PO4 has a greater ability to induce the formation of ABS compared to PEG 400 and PPG 400. ABS consisting of K3PO4 also have a high potential for the extraction of theobromine, with extraction efficiencies ranging between 96.4 and 99.9 %. Based on the most promising ILs for the purification step, they were further used in aqueous solution to extract theobromine from cocoa beans, with extraction yields ranging between 4.5% and 6.5 wt%. Finally, ABS were applied to the aqueous solutions containing theobromine from the cocoa extract, with extraction efficiencies ranging between 96.7 and 99.0%.

Conditions for observing IR chemiluminescence and the role of condensation in metal oxidation reactions

Infrared chemiluminescence (IRCL) studies of cw metal oxidation reactions wherein metal atoms entrained in a carrier gas were mixed with an oxidizer by means of a nozzle system are described. One goal of the work was to determine the vibrational distribution of the product molecule produced by the chemical reaction. In order to observe IRCL it was important to operate the system at the appropriate P-T point in the phase diagram of both the metal and metal salt, otherwise rapid condensation quenched any IRCL that was present. If the nucleation rate was greater 1010 3 than ~ cm-sec-I, then only "black body" radiation could be seen from the reaction. Most of the studies were on the Li/I2 system which is unique in that the phase diagrams of Li and LiI in the P-T ranges of interest are almost identical. This property permitted a relatively easy control with respect to condensation and the measurement of IRCL in the 10-28 um range for the excited LiI molecule.